EP3808810B1 - Matières de moulage thermoplastiques pour un procédé de rotomoulage - Google Patents

Matières de moulage thermoplastiques pour un procédé de rotomoulage Download PDF

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EP3808810B1
EP3808810B1 EP20201941.0A EP20201941A EP3808810B1 EP 3808810 B1 EP3808810 B1 EP 3808810B1 EP 20201941 A EP20201941 A EP 20201941A EP 3808810 B1 EP3808810 B1 EP 3808810B1
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component
weight
repeating units
resin composition
components
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EP3808810A1 (fr
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Stephan Gschwind
Peter Rath
Ingo Landen
Christian Ruthard
Hannes KERSCHBAUMER
Bianca WILHELMUS
Norbert Niessner
Klaus Terlau
Viktor WIEBE
Lars-Hilmar Herbst
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Ineos Styrolution Group GmbH
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Ineos Styrolution Group GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/06—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould about two or more axes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B29K2025/04—Polymers of styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to thermoplastic molding compositions for rotomolding processes and moldings produced by a rotational molding process ("rotomolding").
  • the invention also relates to the use of thermoplastic (resin) compositions containing amorphous (co)polymers based on aromatic vinyl monomers, semi-crystalline polymers and a compatibilizer for the production of molded articles by a rotary molding process, and a method for producing a molded article by a rotational molding process using these thermoplastic compositions, and a molded article produced by a rotational molding process using these thermoplastic compositions.
  • Rotational melting processes have been used for years to produce moldings of various sizes from plastics.
  • the shaped bodies are typically hollow bodies made from thermoplastic polymers.
  • a thermoplastic resin composition is placed in the shaping part of a heatable tool, which is rotated about two mutually perpendicular axes of rotation while being heated.
  • the thermoplastic composition is melted and pressed against the inner walls of the shaping part of the heatable tool. This leads to an even distribution of the composition over the inner walls.
  • a hollow molded body with a (relatively) constant wall thickness can be removed from the shaping part.
  • Rotational melting processes (rotomolding, rotational molding or rotation casting), are used e.g. in " Plastics chemistry for engineers, from synthesis to application” (W. Kaiser, 2nd edition, Hanser Verlag 2007; pages 190-191 ) described.
  • Alternative polar polymers also have application disadvantages, such as polyvinyl chloride (PVC), which can split off HCl under thermal stress, and polyethylene terephthalate (PET), which, if not completely pre-dried, can be degraded in the rotary melting process.
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • Styrene (co)polymers have been known for decades. They are more polar than polyethylene, so that in principle they can be better painted. They are mostly amorphous, so that the disadvantages of partially crystalline materials can be reduced. However, the problem with styrene (co)polymers is that they have hitherto not appeared to be well suited to rotary melting processes due to the often low flowability, oxidation sensitivity and brittleness of the materials.
  • thermoplastic compositions molding materials
  • amorphous and partially crystalline polymer components show advantages over the abovementioned polymers in the rotational molding process.
  • thermoplastic composition used for the production of a shaped body and for use in the rotational molding process are explained in more detail below.
  • the use of similar molding compounds for the production of injection molded parts by an injection molding process is, for example, in WO 2013/104528 disclosed.
  • thermoplastic compositions used according to the invention often contain 5 to 60% by weight, preferably 8 to 55% by weight, particularly preferably 10 to 50% by weight, very particularly preferably 12 to 30% by weight 23% by weight, based on the total weight of components (A), (B), (C) and (D), of at least one amorphous thermoplastic (co)polymer. This contains repeating units derived from at least one aromatic vinyl monomer.
  • the repeating units derived from at least one aromatic vinyl monomer are preferably monomers selected from the group consisting of styrene and methylated styrenes such as alpha-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene.
  • Particularly preferred aromatic vinyl monomers here are styrene and alpha-methyl styrene, in particular styrene.
  • thermoplastic composition with 5 to 60% by weight, preferably 8 to 55% by weight, particularly preferably 10 to 50% by weight, very particularly preferably 12 to 30% by weight, is often used 23% by weight based on the total weight of components (A), (B), (C) and (D), at least an amorphous thermoplastic (co)polymer containing repeating units derived from styrene.
  • SAN is often used.
  • Component (A) preferably contains further repeating units in addition to the repeating units derived from at least one aromatic vinyl monomer. These additional repeat units can be derived, for example, from vinyl cyanide monomers, alkyl acrylate monomers, alkyl methacrylate monomers, alkyl acrylamide monomers, and/or butadiene monomers. In addition to the repeating units originating from at least one aromatic vinyl monomer, component (A) particularly preferably additionally contains repeating units originating from at least one vinyl cyanide monomer, in particular acrylonitrile.
  • thermoplastic composition with 5 to 60% by weight, preferably 8 to 55% by weight, particularly preferably 10 to 50% by weight, very particularly preferably 12 to 30% by weight, is often used 23% by weight, based on the total weight of components (A), (B), (C) and (D), of at least one amorphous thermoplastic copolymer containing repeating units derived from styrene and repeating units derived from acrylonitrile .
  • the at least one (co)polymer of component (A) can be both an ungrafted (co)polymer (resin) and a grafted (co)polymer, or a mixture of ungrafted and grafted (Co -) act polymer. Often z. B. a SAN resin and one or more acrylate rubbers are used.
  • sub-component (A1) ungrafted copolymers containing repeating units derived from vinyl aromatic monomer and repeating units derived from vinyl cyanide monomer are used.
  • Styrene copolymers are preferred, these styrene copolymers being particularly preferably composed of two or more monomers from the group of styrene, acrylonitrile and methylstyrene.
  • SAN styrene-acrylonitrile copolymers
  • examples of the sub-component (A1) are common copolymer matrices such. B.
  • styrene-acrylonitrile copolymers produced by bulk polymerisation, emulsion or solution polymerisation, see for example Luran® from INEOS Styrolution (Frankfurt). Mixtures of matrices are also suitable, for example as in Ullmann's Encyclopedia of Industrial Chemistry (VCH-Verlag, 5th edition, 1992, p. 633 f .) described.
  • subcomponent (A1) are styrene copolymers, these styrene copolymers being built up from two or three monomers from the group of styrene, acrylonitrile and/or ⁇ -methylstyrene.
  • the subcomponent (A1) is preferably prepared from the components acrylonitrile and styrene and/or ⁇ -methylstyrene by bulk polymerization or in the presence of one or more solvents. Copolymers with molecular weights Mw of 15,000 to 300,000 g/mol are preferred, the molecular weights z. B. can be determined by light scattering in tetrahydrofuran (GPC with UV detection).
  • the sub-component (A1) can also be obtained by copolymerization of acrylonitrile, styrene and ⁇ -methylstyrene.
  • the copolymer of styrene and acrylonitrile is particularly preferably used.
  • the number-average molecular weight (Mn) of sub-component (A1) is preferably from 15,000 to 150,000 g/mol (determined by means of GPC with UV detection).
  • the viscosity (VZ) of the sub-component (A1) is (measured according to DIN 53726 at 25° C. in a 0.5% strength by weight solution in DMF) z. B. from 50 to 120 ml/g.
  • the sub-component (A1) can be prepared by bulk polymerization or solution polymerization in, for example, toluene or ethylbenzene, using a process as described, for example, in Kunststoff-Handbuch, Vieweg-Daumiller, Volume V, (polystyrene), Carl-Hanser-Verlag, Kunststoff 1969, pages 122 f., lines 12 ff . is described.
  • graft rubbers comprising a rubber-like backbone and a graft containing repeating units derived from aromatic vinyl monomer and repeating units derived from vinyl cyanide monomer grafted onto the backbone are used.
  • Suitable graft bases are diene rubbers based on dienes, such as e.g. B. butadiene or isoprene, alkyl acrylate rubbers based on alkyl esters of acrylic acid, such as n-butyl acrylate and 2-ethylhexyl acrylate, EPDM rubbers based on ethylene, propylene and a diene, silicone rubbers based on polyorganosiloxanes, or mixtures of these rubbers.
  • diene rubbers based on dienes such as e.g. B. butadiene or isoprene
  • alkyl acrylate rubbers based on alkyl esters of acrylic acid such as n-butyl acrylate and 2-ethylhexyl acrylate
  • EPDM rubbers based on ethylene, propylene and a diene EPDM rubbers based on ethylene, propylene and a diene
  • Alkyl acrylate-based rubbers and butadiene-based rubbers, in particular alkyl acrylate-based rubbers, are preferred as the graft base.
  • a graft rubber with n-butyl acrylate as the graft base is used as subcomponent (A2).
  • the graft layer is preferably made up of styrene and acrylonitrile and optionally ⁇ -methylstyrene, ethyl acrylate and/or methylacrylamide.
  • graft rubbers of subcomponent (A2) and their production reference is made to the description in Ullmann's Encyclopedia of Industrial Chemistry 5th edition, VCH, 1992, pages 633f . referred.
  • a particularly preferred subcomponent (A2) is a graft polymer composed of a graft base, in particular a crosslinked diene or alkyl acrylate graft base, and one or more grafts, in particular one or more styrene or acrylonitrile grafts.
  • the graft in subcomponent (A2) is prepared from, based on the total weight of the graft, 60 to 85% by weight of styrene and 15 to 40% by weight of acrylonitrile.
  • Subcomponent (A2) is preferably a mixture of at least one finely divided graft rubber (A21) and at least one coarsely divided graft rubber (A22), which leads to an at least bimodal particle size distribution of subcomponent (A2).
  • the finely divided graft rubber (A21) preferably has an average particle size (weight average) of 40 to 150 nm, particularly preferably from 60 to 120 nm, very particularly preferably from 80 to 100 nm.
  • the coarsely divided graft rubber (A22) preferably has an average particle size ( Weight average) from 300 to 800 nm, particularly preferably from 400 to 650 nm, most preferably from 450 to 550 nm W. Scholtan and H. Lange, Colloid-Z, and Z.-Polymere 250 (1972), pages 782 to 796 , to be determined.
  • the weight ratio of (A21):(A22) is preferably between 30:70 and 70: 30, more preferably between 40:60 and 60:40, most preferably between 45:55 and 55:45.
  • component (A) comprises a styrene-acrylonitrile copolymer (SAN) as sub-component (A1) and an acrylonitrile-styrene-butyl acrylate graft rubber (ASA) and/or an acrylonitrile-butadiene-styrene graft rubber (ABS ), preferably an ASA graft rubber, as sub-component (A2).
  • SAN styrene-acrylonitrile copolymer
  • ASA acrylonitrile-styrene-butyl acrylate graft rubber
  • ABS acrylonitrile-butadiene-styrene graft rubber
  • the weight ratio of (A1):(A2) is preferably between 30:70 and 70:30, particularly preferably between 40:60 and 60:40, very particularly preferably between 45:55 and 55:45. In a preferred embodiment, 23% by weight SAN and 24% by weight ASA are used.
  • thermoplastic resin compositions used according to the invention contain as component (B) 30 to 90% by weight, preferably 35 to 85% by weight, particularly preferably 40 to 80% by weight, very particularly preferably 60 to 78% by weight based on the total weight of components (A), (B), (C) and (D), at least one semi-crystalline polymer.
  • the partially crystalline polymer is preferably selected from the group consisting of partially crystalline polyethylene, partially crystalline polypropylene, partially crystalline polyester and partially crystalline polyamide.
  • a polyamide PA-6, for example, is often used.
  • partially crystalline means that the polymer is not completely crystalline and is not amorphous.
  • the crystalline fraction of the partially crystalline polymer that can be determined by means of X-ray diffraction (X-ray diffractometry) is typically between 10 and 90%, preferably between 15 and 80%, particularly preferably between 20 and 50%.
  • Component (B) is particularly preferably a partially crystalline polyamide, which can be homopolyamides, copolyamides or mixtures thereof.
  • the polyamides of the thermoplastic resin composition used according to the invention generally have a viscosity number of 70 to 350, preferably 70 to 170 ml/g, determined in a 0.5% by weight solution in 96% by weight sulfuric acid at 25.degree according to DIN EN ISO 307:2017.
  • polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.
  • Alkanedicarboxylic acids having 4 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and/or isophthalic acid may be mentioned here as acids.
  • Particularly suitable diamines are alkanediamines having 4 to 12, in particular 6 to 8, carbon atoms and m-xylylenediamine, di(4-aminophenyl)methane, di(4-aminocyclohexyl)methane, 2,2-di(4-aminophenyl). )-propane, 2,2-di-(4-aminocyclohexyl)-propane or 1,5-diamino-2-methyl-pentane.
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.
  • Polyamides that are also suitable are obtainable from ⁇ -amino-alkyl nitriles such as, for example, amino-capronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66). so-called direct polymerization in the presence of water, such as in the DE-A 10313681 , EP-A 1198491 and EP-A 922065 described.
  • ⁇ -amino-alkyl nitriles such as, for example, amino-capronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66). so-called direct polymerization in the presence of water, such as in the DE-A 10313681 , EP-A 1198491 and EP-A 922065 described.
  • polyamide 46 polyamide 4,6
  • Manufacturing processes for polyamides of this structure are, for example, in the EP-A 038094 , EP-A 038582 and EP-A 039524 described.
  • those partially aromatic copolyamides such as PA 6/6T and PA 66/6T have proven particularly advantageous whose triamine content is less than 0.5, preferably less than 0.3% by weight (see EP-A 299444 ).
  • the preparation of the preferred partially aromatic copolyamides with a low triamine content can be carried out according to the EP-A 129195 and EP-A 129196 described procedures.
  • the non-exhaustive list below includes the polyamides mentioned and other polyamides A) and the monomers present. These play a role for the invention if they have a crystalline content of between 10 and 90%, preferably between 15 and 80%, particularly preferably between 20 and 50%.
  • thermoplastic resin compositions used according to the invention can contain one or more polyamides having, based on the total component B, 0.1-0.2% by weight of triacetonediamine (TAD) end groups.
  • TAD triacetonediamine
  • polyamide 6 is used as component (B). This can be used, for example, in an amount of 46% by weight.
  • the thermoplastic resin compositions used according to the invention contain 0.5 to 10% by weight, preferably 1 to 8% by weight, particularly preferably 2 to 7% by weight, very particularly preferably 3 to 6% by weight. %, based on the total weight of components (A), (B), (C) and (D), of at least one copolymeric compatibilizer which is suitable for improving the compatibility of component (A) and component (B). Two different compatibilizers are often used.
  • suitable compatibilizers are copolymers containing repeating units (C1) derived from at least one aromatic vinyl monomer, repeating units (C2) derived from at least one monomer selected from the group consisting of C 2 - to C 12 -alkyl methacrylates, C 2 - to C 12 - alkyl acrylates and vinyl cyanides, and repeating units (C3) derived from at least one ethylenically unsaturated dicarboxylic acid or anhydride.
  • C1 derived from at least one aromatic vinyl monomer
  • C2 derived from at least one monomer selected from the group consisting of C 2 - to C 12 -alkyl methacrylates, C 2 - to C 12 - alkyl acrylates and vinyl cyanides
  • C3 repeating units
  • the compatibilizer is preferably a copolymer containing repeating units (C1) originating from at least one aromatic vinyl monomer, preferably styrene, repeating units (C2) originating from at least one vinyl cyanide monomer, preferably acrylonitrile, and repeating units (C3 ) derived from at least one ethylenically unsaturated dicarboxylic acid or an ethylenically unsaturated dicarboxylic acid anhydride, preferably maleic anhydride.
  • Particularly preferred as component (C) are copolymers of styrene, acrylonitrile and maleic anhydride.
  • the amount of repeating units originating from maleic anhydride (MA) in component (C) can vary within wide limits and is generally 0.2 to 4% by weight, preferably 0.4 to 3% by weight, in particular preferably 0.8 to 2.3% by weight. Particularly good mechanical properties in terms of tensile strength and impact strength are achieved in these areas. For example, 2% by weight of S-AN-MSA is suitable.
  • Component (C) can be prepared in a manner known per se.
  • a suitable method is to dissolve the component (C) monomer components, e.g. B. styrene, maleic anhydride or acrylonitrile in a suitable solvent, for. B. Methyl ethyl ketone (MEK).
  • MEK Methyl ethyl ketone
  • One or optionally more chemical initiators are added to this solution. Suitable initiators are e.g. e.g. peroxides.
  • the mixture is then polymerized at elevated temperature for several hours.
  • the solvent and the unreacted monomers are then removed in a manner known per se.
  • component (C1) aromatic vinyl monomer
  • component (C2) e.g. B. the acrylonitrile monomer in component (C) is preferably between 80:20 and 50:50.
  • an amount of aromatic vinyl monomer (C1) corresponding to the amount of aromatic vinyl monomer in component (B) is preferably selected.
  • the copolymers of component (C) generally have molecular weights Mw in the range from 30,000 to 500,000 g/mol, preferably from 50,000 to 250,000 g/mol, in particular from 70,000 to 200,000 g/mol, determined by GPC using tetrahydrofuran (THF) as Eluent and with polystyrene calibration.
  • Mw molecular weights in the range from 30,000 to 500,000 g/mol, preferably from 50,000 to 250,000 g/mol, in particular from 70,000 to 200,000 g/mol, determined by GPC using tetrahydrofuran (THF) as Eluent and with polystyrene calibration.
  • THF tetrahydrofuran
  • styrene-N-phenylmaleimide-maleic anhydride terpolymers can also be used.
  • the thermoplastic resin composition used according to the invention comprises up to 10% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 9% by weight, particularly preferably 1 to 6% by weight , e.g. 5% by weight, based on the total weight of components (A), (B), (C) and (D), further additive(s). These components (D) are different from components (A), (B) and (C).
  • Component (D) preferably comprises 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.3 to 4% by weight, based on the total weight of components (A), (B), (C) and (D), a flow improver, preferably a flow improver based on acrylates.
  • Alkyl acrylate oligomers with a weight-average molecular weight in the range from 1200 to 4000 g/mol, preferably 1500 to 2000 g/mol, are preferably used. The molecular weight is determined by means of gel permeation chromatography, with THF preferably being used as the eluent. The calibration is carried out with polystyrene standards.
  • the alkyl acrylates are preferably C 1-12 alkyl acrylates, especially C 4-8 alkyl acrylates.
  • butyl acrylates or ethylhexyl acrylates especially preferably n-butyl acrylate.
  • the alkyl acrylate oligomers are prepared by the known polymerization processes.
  • the polybutyl acrylates are preferably prepared by free-radical polymerization, it being possible for azo or peroxide compounds to be used as initiators.
  • the polybutyl acrylates can contain up to 40% by weight, preferably up to 20% by weight, of one or more copolymerizable monomers.
  • Preferred comonomers are selected from the group consisting of acrylates, methacrylates, styrene or its derivatives, maleic anhydride, acrylonitrile and mixtures thereof.
  • Polybutyl acrylates, which are liquid at room temperature, are preferably used as flow improvers.
  • component (D) Other additives that can be contained in component (D) are, for example, dicarboxylic acid anhydrides, fillers, processing aids, nucleating agents, stabilizers (e.g. HALS) and antioxidants, antioxidants. Mention agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, flame retardants, antistatic agents, dyes and pigments and plasticizers.
  • dicarboxylic acid anhydrides for example, dicarboxylic acid anhydrides, fillers, processing aids, nucleating agents, stabilizers (e.g. HALS) and antioxidants, antioxidants. Mention agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, flame retardants, antistatic agents, dyes and pigments and plasticizers.
  • Agents against thermal decomposition or oxidation retardants are usually metal halides (chlorides, bromides, iodides) derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Stabilizers suitable as component D are the usual hindered phenols, but also "vitamin E” or compounds of analogous structure. Benzophenones, resorcinols, salicylates, benzotriazoles and other compounds are also suitable. These are usually used in amounts of 0 to 2% by weight, preferably 0.01 to 2% by weight (based on the total weight of the molding compositions according to the invention). The molding compositions often do not contain any stabilizers in component D.
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or higher fatty acids in general, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms. If present, the amounts of these additives are in the range from 0.05 to 1% by weight (based on the total weight of the molding compositions according to the invention).
  • Silicone oils, oligomeric isobutylene or similar substances can also be used as additives.
  • the usual amounts, if present, are from 0.05 to 5% by weight (based on the total weight of the molding compositions according to the invention).
  • Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
  • Processing aids and stabilizers, lubricants and antistatic agents are usually used in amounts of 0 to 2% by weight, preferably 0.01 to 2% by weight (based on the total weight of the molding compositions according to the invention).
  • component (D) contains at least one light stabilizer, for example a stabilizer of the HALS type, in particular bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate. This is preferably in an amount of 0.1 to 3% by weight, particularly preferably 0.5 to 2% by weight, based on the total weight of components (A), (B), (C) and (D ) contain.
  • a stabilizer of the HALS type in particular bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • component (D) contains at least one antioxidant, for example a sterically hindered phenol derivative, in particular octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. This is preferably in an amount of 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on the total weight of components (A), (B), (C) and (D) included.
  • antioxidant for example a sterically hindered phenol derivative, in particular octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
  • component (D) contains at least one heat stabilizer, for example a derivative of a thioether.
  • Dioctadecyl 3,3'-thiodipropionate for example, is suitable. This is preferably in an amount of 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on the total weight of components (A), (B), (C) and (D) included.
  • component (D) contains at least one light stabilizer, for example a stabilizer of the HALS type, in particular bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate in an amount of 0.1 to 3% by weight.
  • a stabilizer of the HALS type in particular bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate in an amount of 0.1 to 3% by weight.
  • -% particularly preferably from 0.5 to 2% by weight, based on the total weight of components (A), (B), (C) and (D), of at least one antioxidant, for example a sterically hindered phenol derivative, in particular octadecyl -3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate in an amount of 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight based on the total weight of components (A), (B), (C) and (D) and at least one heat stabilizer, for example a derivative of a thioether, in particular a dioctadecyl 3,3'-thiodipropionate in an amount of 0.01 to 1 wt. -%, particularly preferably from 0.05 to 0.5% by weight, based on the total weight of components (A), (B), (C) and (D).
  • antioxidant for example a sterically hindered phenol derivative, in particular octa
  • a maleic acid-functionalized ethylene copolymer eg Exxelor® VA 1801
  • component D eg Exxelor® VA 1801
  • thermoplastic resin compositions used according to the invention are prepared according to methods known per se by mixing the components. It can be advantageous to pre-mix individual components. Mixing the components in solution while removing the solvent is also possible.
  • suitable organic solvents are chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene and aromatic hydrocarbons such as toluene. Preferably without chlorinated solvents worked.
  • the solvent mixtures can be evaporated, for example, in evaporation extruders.
  • the components (A), (B), (C) and (D), for example dry, can be mixed by any known method.
  • the mixing preferably takes place at temperatures of from 200 to 320° C. by extruding, kneading or rolling the components together, the components having optionally been isolated beforehand from the solution obtained in the polymerization or from the aqueous dispersion.
  • the thermoplastic resin composition used in the present invention has a disperse phase and a continuous phase.
  • the average domain size of the disperse phase is preferably less than 10 ⁇ m, more preferably less than 5 ⁇ m, very preferably less than 2 ⁇ m, in particular less than 1 ⁇ m. With such domain sizes, the compatibility of the phases is improved particularly effectively.
  • the domain size is measured by electron microscopy on ultramicrotome thin films contrasted with RuO 4 .
  • steps (III), (IV) and (V) can be carried out in a vacuum and/or under an inert gas, preferably nitrogen or argon, particularly preferably nitrogen, since this reduces the oxidation and associated yellowing of the shaped bodies.
  • an inert gas preferably nitrogen or argon, particularly preferably nitrogen
  • the subject of the present invention is a molded article produced by a rotational molding process using a thermoplastic resin composition as described above.
  • the shaped body is preferably produced under vacuum and/or inert gas, preferably nitrogen or argon, particularly preferably nitrogen.
  • the shaped body is particularly preferably additionally coated.
  • the components were mixed in a twin-screw extruder at a melt temperature of 240°C to 260°C.
  • the melt was passed through a water bath and granulated.
  • the granules obtained were brought to a temperature below the lowest glass transition temperature T g of all components contained (below -100° C.) using a liquid nitrogen coolant in a cryogenic mill and ground to a powder with a particle size below 500 ⁇ m.
  • Shaped bodies were produced from the powder by rotomolding in a conventional rotomolding device with a mold divided into two mold halves at mold temperatures between 250 and 300° C. and running times of 15 minutes to 45 minutes.
  • the powdery resin composition was placed in a mold half and the mold was closed by fitting the two mold halves together.
  • the mold can optionally be placed under nitrogen or evacuated before being placed in a heating oven, biaxially rotated according to standard machine parameters and heated to operating temperature. After the end of the term, the Take the mold out of the oven and let it cool down. The mold was opened by separating the two mold halves and the resulting molding was removed.
  • thermoplastic resin composition a mixture of 23% by weight of component A1, 12% by weight of component A21, 12% by weight of component A22; 46% by weight of component B, 2% by weight of component C (styrene-acrylonitrile-maleic anhydride terpolymer with styrene:acrylonitrile:MSA of 75.5:23.5:1.0) and 5% by weight component D (ie maleic acid functionalized ethylene copolymer such as Exxelor® VA 1801 from ExxonMobil).
  • component C styrene-acrylonitrile-maleic anhydride terpolymer with styrene:acrylonitrile:MSA of 75.5:23.5:1.0
  • component D ie maleic acid functionalized ethylene copolymer such as Exxelor® VA 1801 from ExxonMobil.
  • the color of the molding had the color of the starting material.
  • the surface was even and smooth. No porosity was found.
  • the molded body was translucent and mechanically stable: in the drop test from a height of 1.5 m, elastic properties were determined.
  • Example 1 was repeated with the difference that the thermoplastic composition used was a mixture of 10% by weight of component A1, 6% by weight of component A21, 4% by weight of component A22, 70% by weight of component B , 3.5% by weight of component C and 6.5% by weight of component D was used.
  • the thermoplastic composition used was a mixture of 10% by weight of component A1, 6% by weight of component A21, 4% by weight of component A22, 70% by weight of component B , 3.5% by weight of component C and 6.5% by weight of component D was used.
  • the color of the molding had the color of the starting material. The surface was even and smooth. No porosity was found.
  • Example 2 was repeated with the difference that the hollow spherical mold was not flushed with nitrogen but instead was evacuated.
  • the color of the molding had the color of the starting material. The surface was even and smooth. No porosity was found.
  • Example 2 was repeated with the difference that the hollow spherical mold was not flushed with nitrogen.
  • the color of the molding was only slightly yellow in comparison to the starting material. No surface porosity was observed. The surface was even and smooth.
  • Example 1 was repeated with the difference that the commercially available acrylate-styrene-acrylonitrile copolymer Luran® S 778 T from INEOS Styrolution was used instead of the thermoplastic resin composition.
  • the powder could not be processed in rotational molding due to irregular melting. An inhomogeneous inner surface of the molded part was established. The molding was severely yellowed and highly fragile.
  • the molding from Example 2 was coated with a primer tailored to polyamide (PA) (Hydroprimer 3941072A, Akzo Nobel) and then first coated with Hydrobasis paint Obsidian BLACK MB, Akzo Nobel, and then coated with Clear Paint Finish 7807096, Akzo Nobel.
  • PA primer tailored to polyamide
  • the molding was subjected to a temperature change test in accordance with DBL 5416 A.2.10 (test duration 3 cycles; 1 cycle consists of 15 hours at 105°C, 30 minutes at 23 ⁇ 2°C, 8 hours at -40°C, 30 Minimum 23 ⁇ 2°C). Assessment was made 1 and 24 hours after the end of the test with subsequent adhesion test (steam jet test) in accordance with DBL 5416 2.10.1. The paint adhesion was rated KW 0 after 1 hour and after 24 hours.
  • Example 5 was repeated with the difference that a primer 39112702C, Akzo Nobel, matched to acrylonitrile butadiene styrene (ABS) was used.
  • the paint adhesion was rated KW 1 after 1 hour and after 24 hours.
  • Shaped bodies were produced from the main component B by means of an injection molding process.
  • the shaped body was painted according to Example 5 and examined.
  • the paint adhesion was rated KW 2-3.
  • Comparative example 2 was repeated with the difference that the ABS-matched primer 39112702C, Akzo Nobel, was used.
  • the paint adhesion was rated KW 4 after 1 hour and after 24 hours.
  • the shaped body from Comparative Example 1 was coated according to Example 5 and subjected to the temperature cycling test.
  • the shaped body softened during the temperature change test and could not be examined.
  • Shaped bodies were produced from the material of example 2 by means of injection molding processes.
  • the shaped body was painted according to Example 5 and examined.
  • the paint adhesion was rated KW 1.
  • Comparative Example 5 was repeated except that Akzo Nobel's ABS matched primer 39112702C was used in place of the PA matched primer.
  • the paint adhesion was rated KW 3 after 1 hour and after 24 hours.
  • moldings made from the resin composition used according to the invention also after use of the primer tailored to ABS are easier to paint using the injection molding process than the moldings made of polyamide (comparative example 3), but nevertheless have poorer paint adhesion than the moldings produced according to the invention by means of rotomolding (example 6).

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  • Chemical Kinetics & Catalysis (AREA)
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Claims (15)

  1. Utilisation d'une composition de résine thermoplastique contenant:
    a) de 5 à 60 % en poids, exprimés par rapport au poids total des composants (A), (B), (C) et (D), d'au moins un (co)polymère thermoplastique amorphe en tant que composant (A) contenant des motifs répétitifs dérivés d'au moins un monomère vinylique aromatique,
    b) de 30 à 90 % en poids, exprimés par rapport au poids total des composants (A), (B), (C) et (D), d'au moins un polymère semi-cristallin comme composant (B);
    c) de 0,5 à 10 % en poids, exprimés par rapport au poids total des composants (A), (B), (C) et (D), d'au moins un promoteur de compatibilité avec les copolymères comme composant (C), lequel est approprié pour améliorer la compatibilité du composant (A) et du composant (B); et
    d) de 0 à 10 % en poids, exprimés par rapport au poids total des composants (A), (B), (C) et (D), d'additif(s) supplémentaire(s) en tant que composant (D);
    dans laquelle la somme en % en poids des composants (A), (B), (C) et (D) donne 100 % en poids,
    pour la fabrication d'un corps moulé par un procédé de rotomoulage.
  2. Utilisation selon la revendication 1, dans laquelle le composant (A) contient, outre des motifs répétitifs dérivés d'au moins un monomère vinylique aromatique, des motifs répétitifs dérivés d'au moins un monomère de cyanure de vinyle.
  3. Utilisation selon la revendication 1 ou 2, dans laquelle le composant (A) comprend un mélange de :
    a1) de 20 à 60 % en poids, exprimés par rapport au poids total des sous-composants (A1) et (A2), d'un copolymère non greffé en tant que sous-composant (A1), contenant des unités répétées dérivées du monomère vinylique aromatique, et des unités répétées dérivées du monomère de cyanure de vinyle, et
    a2) de 40 à 80 % en poids, exprimés par rapport au poids total des sous-composants (A1) et (A2), d'au moins un caoutchouc greffé en tant que sous-composant (A2), comprenant une base de greffage de type caoutchouc et une couche de greffage greffée sur l'unité de greffage contenant des unités répétées dérivées de monomère vinylique aromatique, et des unités répétitives dérivées du monomère de cyanure de vinyle.
  4. Utilisation selon la revendication 3, dans laquelle la base de greffage du composant (A2) est choisie dans le groupe constitué par du caoutchouc à base d'un acrylate d'alkyle et d'un caoutchouc à base de butadiène.
  5. Utilisation selon la revendication 3 ou 4, dans laquelle dans le composant (A) le sous-composant (A1) est un copolymère styrène-acrylonitrile (SAN), et le sous-composant (A2) est un caoutchouc greffé acrylonitrile-styrène-butyle (ASA) et/ou un caoutchouc greffé acrylonitrile-butadiène-styrène (ABS), de préférence un caoutchouc greffé ASA.
  6. Utilisation selon au moins l'une des revendications 1 à 5, dans laquelle le composant (B) est choisi dans le groupe constitué par le polyéthylène semi-cristallin, le polypropylène semi-cristallin, le polyester semi-cristallin et le polyamide semi-cristallin.
  7. Utilisation selon au moins une des revendications 1 à 6, dans laquelle le composant (B) est un polyamide semi-cristallin, de préférence un polyamide-6 semi-cristallin.
  8. Utilisation selon au moins une des revendications 1 à 7, dans laquelle le composant (C) contient des motifs répétitifs (C1) dérivés d'au moins un vinylmonomère aromatique, de préférence du styrène, des motifs répétitifs (C2) dérivés d'au moins un monomère de cyanure de vinyle, de préférence l'acrylonitrile, et des motifs répétitifs (C3) dérivés d'au moins un acide dicarboxylique éthyléniquement insaturé ou d'un anhydride dicarboxylique éthyléniquement insaturé, de préférence l'anhydride maléique.
  9. Utilisation selon au moins une des revendications 1 à 8, dans laquelle la composition de résine thermoplastique présente une phase dispersée et une phase continue, et la dimension moyenne de la phase dispersée est inférieure à 10 µm, de préférence inférieure à 5 µm, plus préférentiellement inférieure à 2 µm, tout particulièrement de préférence inférieure à 1 µm.
  10. Utilisation selon au moins une des revendications 1 à 9, dans laquelle le composant (D) comprend un amplificateur de flux polymère, de préférence un améliorant, à base d'acrylates, en une quantité de 0,1 à 5 % en poids, exprimés par rapport au poids total des composants (A), (B), (C) et (D).
  11. Procédé de production d'un corps moulé par un procédé de fusion par rotation, comprenant les étapes consistant à:
    (I) introduire une composition de résine thermoplastique, telle que décrite dans au moins une des revendications 1 à 10, dans la partie de formage d'un dispositif pour la mise en oeuvre d'un procédé de fusion par rotation;
    (II) commencer au moins la rotation biaxiale de la partie de formage du dispositif , par la mise en oeuvre du procédé de fusion par rotation contenant la composition de résine thermoplastique;
    (III) chauffage de la composition de résine thermoplastique de la partie de formage du dispositif pour la mise en oeuvre du procédé de fusion par rotation, à une température supérieure à la plage de fusion de la composition de résine thermoplastique;
    (IV) réalisation d'une distribution uniforme de la composition de résine thermoplastique fondue dans la partie de formage du dispositif pour la mise en oeuvre du procédé de fusion par rotation;
    (V) refroidissement à une température de 10- 40°C de la composition de résine thermoplastique répartie dans la partie de formage du dispositif pour la mise en oeuvre du procédé de fusion par rotation;
    (VI) arrêt de la rotation de la partie de formage du dispositif pour la mise en oeuvre du procédé de fusion par rotation;
    (VII) retrait du corps moulé de la partie de formage du dispositif pour la mise en oeuvre du procédé de fusion par rotation.
  12. Procédé selon la revendication 11, dans lequel au moins les étapes (III), (IV) et (V) sont réalisées sous vide et/ou sous gaz protecteur, de préférence d'azote ou d'argon, notamment, préférentiellement, d'azote.
  13. Corps moulé, préparé par un procédé de fusion par rotation (rotomoulage), en utilisant une composition de résine thermoplastique telle que décrite dans au moins une des revendications 1 à 10.
  14. Corps moulé selon la revendication 13, préparé sous vide et/ou gaz protecteur, de préférence l'azote ou l'argon, plus préférentiellement l'azote.
  15. Corps moulé selon la revendication 13 ou 14, dans lesquelles le corps moulé est en outre laqué.
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